CN100421792C - Method for preparing solid sulfonic acid from reproducible vegetable material - Google Patents
Method for preparing solid sulfonic acid from reproducible vegetable material Download PDFInfo
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- CN100421792C CN100421792C CNB2006100321879A CN200610032187A CN100421792C CN 100421792 C CN100421792 C CN 100421792C CN B2006100321879 A CNB2006100321879 A CN B2006100321879A CN 200610032187 A CN200610032187 A CN 200610032187A CN 100421792 C CN100421792 C CN 100421792C
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- solid sulfoacid
- sulfuric acid
- charing
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Abstract
A process for preparing solid sulfonic acid from the regeneratable vegetative raw material, such as wood bits and bamboobits, includes such steps as drying the vegetative raw material containing cellulose and lignin, breaking, proportionally mixing it with sulfuric acid, stirring at 40-200 deg.C for 1-20 hr, cooling, washing with deionized water until it becomes neutral, baking, proportionally adding sulfonating agent, sulfonating at 30-150 deg.C for 1-20 hr, cooling, washing with deionized water until it becomes neutral, testing no deposition in BaCl2 solution, and baking.
Description
Technical field
The invention belongs to a kind of Preparation of catalysts method, be specifically related to the preparation method of solid sulfoacid.
Background technology
Sulfonic acid is widely used in all kinds of acid catalyzed reactions such as esterification, etherificate, dehydration, hydration, isomery as a kind of strong protonic acid catalyst.
Common solid sulfoacid catalyst has p-methyl benzenesulfonic acid, sulfamic acid, sulfonate resin etc.P-methyl benzenesulfonic acid and catalyzed by amino sulfonic acid agent are in organic reaction, when particularly having water to exist, certain dissolving is all arranged and become liquid acid catalysis, though liquid sulfonic acid acid strength is big, the reactivity height, but have shortcomings such as difficulty is separated, corrosivity is strong, environmental pollution is big.Sulfonate resin is difficult to bear high temperature, and easy broken loss under long-time the stirring.In recent years, there is the people on the mesoporous silicon sill, to introduce sulfydryl, is oxidized to silica-based solid sulfoacid then through silanization, but its preparation process length consuming time, complex operation.
Above solid sulfoacid is as the shortcoming of catalyst except self, and its preparation raw material all be unable to do without mineral resources such as non-reproducible coal and oil.Under energy situation in short supply day by day, this shortcoming will limit the production and the application in their futures.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned prior art, it is raw material (as cotton, fiber crops, bamboo, reed, timber etc.) that a kind of fibre-bearing element that exists in a large number with nature or the renewable plant resources of lignin are provided, less energy consumption, cycle is short, and the renewable plant plant material that meets the Green Chemistry requirement prepares the method for solid sulfoacid.
Principle of the present invention is: the cellulose chain dehydration carbonization in the raw material, and the solid carbon material that obtains having the polycyclic aromatic hydrocarbon structure, and then on aromatic ring, introduce sulfonic group and prepare solid sulfoacid.
The present invention is achieved by the following technical programs.
The present invention includes following steps:
(1), with the raw material drying of fibre-bearing element or lignin, be ground into graininess;
(2), in above-mentioned dried feed, be 3～20: 1 by sulfuric acid and raw material mass ratio, add mass percent and be 65～95% sulfuric acid, constant temperature stirs charing, the time is 1～20h, temperature is 40～200 ℃, product;
(3), add after the above-mentioned product cooling deionized water wash to filtrate for neutral, oven dry, moulding gets the charing particle;
(4), above-mentioned charing particle adds sulfonating agent, the constant temperature sulfonation, temperature is 30～150 ℃, the time is 1～20h, cooling back deionized water wash to filtrate for neutral, BaCl
2Solution detects does not have precipitation, and oven dry obtains solid sulfoacid, and described sulfonating agent is 3～15: 1 with charing granular mass ratio.
The raw material of described fibre-bearing element or lignin is any one or its composition in cotton, fiber crops, bamboo bits, reed, the wood chip; Described sulfuric acid and raw material mass ratio are preferably 6～10: 1; Described constant temperature stirs carbonization temperature and is preferably 60～120 ℃; Described constant temperature stirs carbonization time and is preferably 1～5h; Described sulfonation temperature is preferably 60～120 ℃; The described sulfonation time is preferably 1～7h; Described sulfonating agent is oleum, the concentrated sulfuric acid or chlorosulfonic acid etc.; Described sulfonating agent is 3～10: 1 with charing granular mass ratio.
The advantage of this method is: (1) less energy consumption, the cycle is short, meets the requirement of Green Chemistry.(2) initial feed adopts renewable plant resources cheap and easy to get or processing waste (as wood sawdust, the bamboo bits) to replace the industrial product based on nonrenewable resourceses such as coal, oil, has improved resource utilization, helps slowing down energy crisis.(3) adopt the sulfuric acid catalysis charring in the step 2, shortened reaction time, reduced energy dissipation.
Description of drawings
Fig. 1 is the infrared spectrogram (FT-IR) of cotton charcoal base sulfonic acid.
Fig. 2 is in the cotton charcoal base sulfonic acid preparation process, and the x-ray photoelectron of carbonizing production a and sulfonated products b can spectrogram (XPS).
The specific embodiment
Embodiment 1: get saw bamboo bits 4.0kg, and drying, the sulfuric acid solution 12.64kg of adding 95% stirs, 60 ℃ of isothermal reaction 3h, it is neutral that the cooling back is washed till filtrate with deionized water, dries, and obtains bamboo charcoal 1.39kg.Bamboo charcoal 1.0kg adds 50% (mass percent) chlorosulfonic acid 10kg, and 100 ℃ of constant temperature sulfonation 2h add the deionized water cessation reaction, and it is neutral washing to filtrate, uses BaCl
2Solution detect not to have precipitation, 100 ℃ dry bamboo charcoal base sulfonic acid, titration gets its acid amount and is 2.0mmolg
-1
Embodiment 2: get wood sawdust 4.0kg, add the sulfuric acid 42.7kg of 75% (mass percent), the control carbonization temperature is at 80 ℃, and constant temperature stirring reaction 3h adds deionized water and is washed till filtrate for neutral after the cooling, and oven dry obtains sawmilling charcoal 1.42kg.Get 1.0kg sawmilling charcoal, press mass ratio and add the concentrated sulfuric acid at 7: 1,120 ℃ of sulfonation 2h add the deionized water cessation reaction, and it is neutral washing to filtrate, uses BaCl
2Solution detects does not have precipitation, and 100 ℃ of oven dry obtain sawmilling charcoal base sulfonic acid 1.33kg.Titration gets sulfonic acid acid amount and is 1.82mmolg
-1
Embodiment 3: the cotton 4.0kg of extracting degreasing, the sulfuric acid 40.0kg of adding 80% (mass percent), control carbonization temperature are at 100 ℃, and constant temperature stirring reaction 1h, cooling back deionized water are washed till filtrate and are neutrality, and oven dry obtains cotton charcoal 1.58kg.Get the cotton charcoal of 1.0kg, press mass ratio and add 50% (mass percent) oleum at 5: 1,80 ℃ of sulfonation 2h add the deionized water cessation reaction, and it is neutral washing to filtrate, uses BaCl
2Solution detects does not have precipitation.100 ℃ of oven dry obtain cotton charcoal base sulfonic acid 1.10kg.The cotton charcoal base sulfonic acid acid amount that titration obtains is 2.28mmolg
-1
The cotton charcoal base of products therefrom sulfonic acid is identified and the XPS evaluation through FT-IR, for containing the solid sulfoacid of sulfonic acid group.
From the cotton charcoal base of gained sulfonic acid FT-IR collection of illustrative plates (Fig. 1): 1400cm as can be known
-1～1617cm
-1There is the eigen vibration of aromatic ring, illustrates and contain aromatic ring structure in the product; Be present in 1178cm
-1, 1032cm
-1Two asymmetric, the symmetrical stretching vibration peaks of key of the S=O at place are with 645cm
-1The eigen vibration of the C-S of place singly-bound has illustrated the existence of sulfonic acid group in the product structure.
The cotton charcoal base sulfonic acid XPS collection of illustrative plates of products therefrom (Fig. 2) has contrasted the XPS collection of illustrative plates of carbonizing production a and sulfonated products b in the preparation process, further specify after the sulfonation sulfonic acid group from bond energy and be incorporated into successfully that solid sulfoacid product b compares with carbonizing production a on the solid carbon material, the new peak that occurs+6 valency sulphur at the 168.7eV place illustrates after the sulfonation that sulphur is with (SO in the product
3H) form exists, and product is the solid sulfoacid that contains sulfonic acid group.
Above embodiment is intended to illustrate the present invention rather than limitation of the invention.
Claims (8)
1. the method for a preparing solid sulfonic acid from reproducible vegetable material is characterized in that may further comprise the steps:
A. with the raw material drying of fibre-bearing element or lignin, be ground into graininess;
B. in above-mentioned pulverizing raw material, be 3～20: 1 by sulfuric acid and raw material mass ratio, the adding mass percent is 65～95% sulfuric acid, and constant temperature stirs charing, and the time is 1～20h, and temperature is 40～200 ℃, gets product;
C. add after the cooling of above-mentioned product deionized water wash to filtrate for neutral, oven dry, moulding, the charing particle;
D. above-mentioned charing particle is 3～15: the 1 adding sulfonating agent concentrated sulfuric acid, chlorosulfonic acid or oleum by sulfonating agent and charing granular mass ratio, the constant temperature sulfonation, and temperature is 30～150 ℃, and the time is 1～20h, and it is neutral that cooling back deionized water washs to filtrate, BaCl
2Solution detects does not have precipitation, and oven dry obtains solid sulfoacid.
2. according to the described method for preparing solid sulfoacid of claim 1, the raw material that it is characterized in that fibre-bearing element among the described step a or lignin is any one or its composition in cotton, fiber crops, bamboo bits, reed, the wood chip.
3. according to claim 1 or the 2 described methods that prepare solid sulfoacid, it is characterized in that sulfuric acid and raw material mass ratio are 6～10: 1 among the described step b.
4. according to claim 1 or the 2 described methods that prepare solid sulfoacid, it is characterized in that constant temperature stirring carbonization temperature is 60～120 ℃ among the described step b.
5. according to claim 1 or the 2 described methods that prepare solid sulfoacid, it is characterized in that constant temperature stirring carbonization time is 1～5h among the described step b.
6. according to claim 1 or the 2 described methods that prepare solid sulfoacid, it is characterized in that sulfonation temperature is 60～120 ℃ in the described steps d.
7. according to claim 1 or the 2 described methods that prepare solid sulfoacid, it is characterized in that the sulfonation time is 1～7h in the described steps d.
8. according to claim 1 or the 2 described methods that prepare solid sulfoacid, it is characterized in that sulfonating agent is 3～10: 1 with charing granular mass ratio in the described steps d.
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| CNB2006100321879A CN100421792C (en) | 2006-09-05 | 2006-09-05 | Method for preparing solid sulfonic acid from reproducible vegetable material |
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| CN101289629B (en) * | 2008-06-16 | 2013-03-13 | 南昌大学 | Process for preparing biodiesel by one-step method using biomass based sulfonation charcoal as fatty acid esterification and triglyceride transform esterification catalysts |
| CN102746271A (en) * | 2012-07-31 | 2012-10-24 | 浙江扬帆精细化工有限公司 | Preparation method of 2-isopropyl thioxanthone (ITX) |
| CN103910541B (en) * | 2014-04-11 | 2016-08-17 | 河南工业大学 | A kind of method of sludge composting wooden conditioner surface carbonation |
| CN104311094B (en) * | 2014-10-21 | 2016-01-20 | 华侨大学 | A kind of preparation method of carbon/carbon compound material |
| TWI615398B (en) * | 2015-12-10 | 2018-02-21 | 財團法人工業技術研究院 | Method for preparing sugars |
| CN106938196A (en) | 2015-12-10 | 2017-07-11 | 财团法人工业技术研究院 | Solid catalyst and preparation method of saccharide using the same |
| CN105536818A (en) * | 2016-01-26 | 2016-05-04 | 裴卿 | Preparation method for sulfonic acid type solid acid and method for utilizing waste plastic to prepare fuel oil |
| CN108786916A (en) * | 2018-05-24 | 2018-11-13 | 上海大学 | Sludge carbon-based solid acid and the preparation method and application thereof |
| US11414623B2 (en) * | 2019-05-29 | 2022-08-16 | King Fahd University Of Petroleum And Minerals | Efficient biomass carbon-based solid acid esterification catalyst for producing biodiesel |
| CN114768828B (en) * | 2022-05-31 | 2023-11-17 | 陕西科技大学 | Carbon-based solid acid catalyst CS-SO 3 H, preparation method and application thereof in preparing furfural by converting biomass raw materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043434A (en) * | 1989-01-19 | 1991-08-27 | Westvaco Corporation | Oleum sulfonation of lignins |
| US6060424A (en) * | 1995-09-28 | 2000-05-09 | Westvaco Corporation | High energy density carbons for use in double layer energy storage devices |
| US6284213B1 (en) * | 1998-08-05 | 2001-09-04 | Enichem S.P.A. | Catalyst, process for the production of hydrogen peroxide and its use in oxidation processes |
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2006
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043434A (en) * | 1989-01-19 | 1991-08-27 | Westvaco Corporation | Oleum sulfonation of lignins |
| US6060424A (en) * | 1995-09-28 | 2000-05-09 | Westvaco Corporation | High energy density carbons for use in double layer energy storage devices |
| US6284213B1 (en) * | 1998-08-05 | 2001-09-04 | Enichem S.P.A. | Catalyst, process for the production of hydrogen peroxide and its use in oxidation processes |
Non-Patent Citations (4)
| Title |
|---|
| 常温固体脱色剂的研究生产及应用. 时运铭，沈铁焕，刘树彬，许保恩等.农业与技术，第1期. 1996 |
| 常温固体脱色剂的研究生产及应用. 时运铭，沈铁焕，刘树彬，许保恩等.农业与技术，第1期. 1996 * |
| 植物纤维深加工产品及其应用. 宋国安.化工进展，第4期. 1997 |
| 植物纤维深加工产品及其应用. 宋国安.化工进展，第4期. 1997 * |
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